US4102858A - 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylates and aminocarboxylates and synthetic resin compositions containing the same - Google Patents

2,2,6,6-tetramethyl-4-piperidyl thiocarboxylates and aminocarboxylates and synthetic resin compositions containing the same Download PDF

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US4102858A
US4102858A US05/724,793 US72479376A US4102858A US 4102858 A US4102858 A US 4102858A US 72479376 A US72479376 A US 72479376A US 4102858 A US4102858 A US 4102858A
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polyvinyl chloride
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Motonobu Minagawa
Naohiro Kubota
Toshihiro Shibata
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Adeka Corp
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Argus Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/54—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

  • Hindered 2,2,6,6-tetraalkyl-4-carboxylic acid ester piperidine compounds have been proposed by Murayama et al U.S. Pat. No. 3,640,928 patented Feb. 8, 1972 as light and heat stabilizers for synthetic polymers, such as polyolefins, polyvinyl chloride, polyvinylidene chloride, polyurethanes, and polyamides. These compounds have the general formula: ##STR4## or a salt thereof.
  • R 1 and R 2 which may be the same or different, each are an alkyl group such as methyl, ethyl, isopropyl or dodecyl, or they form, together with the carbon atom to which they are attached, a saturated alicyclic group such as: ##STR5## or a group of the formula ##STR6## n is an integer of 1 to 3 inclusive: and R 3 is an acyl group.
  • the compounds generally employed previously have either been highly colored, such as the nickel compounds (which are normally green) and the 2-hydroxybenzophenones (which are varying shades and intensities of yellow). They also show very little tendency towards sublimation and exudation, and they have an excellent stabilizing action against both heat and light deterioration.
  • Murayama et al patent has been followed by a large number of patent and literature disclosures by Murayama et al and others of compounds including a 2,2,6,6-tetrasubstituted-4-piperidyl group attached to a base molecule of varying structures.
  • R 2 represents hydrogen atom, an aliphatic, aromatic or heterocyclic monoacyl group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an alkoxyalkyl group, an epoxyalkyl group, an alkoxysulfonylalkyl group, N-substituted carbamoyl group, a N-substituted thiocarbamoyl group, a monovalent group from an oxoacid or group ##STR9## in which
  • R 3 represents hydrogen atom, a lower alkyl group or phenyl group and R 4 represents an alkyl group;
  • R 2 represents carbonyl group, an aliphatic or aromatic diacyl group, an alkylene group, an alkenylene group, an alkynylene group, an aralkylene group, a N-substituted dicarbamoyl group or a divalent group from an oxoacid;
  • R 2 represents an aromatic triacyl group or a trivalent group from an oxoacid
  • R 2 represents an aromatic tetraacyl group
  • A represents a group ##STR10## in which R 5 represents hydrogen atom or a lower alkyl group or, when n is 1, R 5 may represent together with R 2 a group ##STR11## in which R 6 represents the same group as defined in R 1 and may be the same or different from R 1 , or a group ##STR12## in which m is 1 or 2 and R 7 represents hydrogen atom or, when n and m are 1, R 7 represents methylene group together with R 2 .
  • X represents oxygen atom or sulfur atom
  • Y represents oxygen atom, sulfur atom or a group of the formula ⁇ N--R" in which R" is hydrogen atom, an alkyl group or a substituted alkyl group;
  • Z represents oxygen atom or a group of the formula >N--R'" is hydrogen atom, an alkyl group or a substituted alkyl group;
  • n is an integer of 1 through 4 inclusive
  • R represents, when n is 1, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a substituted phosphino group or a substituted phosphinyl group, when n is 2, an alkylene group, an alkenylene group, an arylene group, a substituted arylene group, an aralkylene group, an alkylenediphenylene group, a bis-(acyloxyalkylene) group, an alkylene-bis-(oxycarbonylalkyl) group, a dialkylene ether group or a diphenylene ether group, when n is 3, an alkanetriyl group, a tris-(acyloxyalkylene) group, an alkane-tris-(oxycarbonylalkyl) group or a group of the group ##STR14##
  • Murayama et al U.S. Pat. No. 3,940,363 patented Feb. 24, 1976 disclose a further variation in which two 2,2,6,6-tetrasubstituted-4-piperidyl groups are linked together via the ring nitrogen atom to an R' alkylene linking group, which may be interrupted with an oxygen or sulfur atom, an alkenylene group, an alkynylene group, an aralkylene group, an aliphatic diacyl group, a group having the formula: ##STR15## in which n is an integer of 1 or 2 and X is an alkylene group, or o-, m- or p-phenylene group or the carbon atoms of CO groups may be directly joined in the absence of X or a group of the formula: ##STR16## in which Y is an alkylene group or o-, m- or p-phenylene group.
  • R 3 is an alkyl group of from one to twenty atoms
  • R 4 is hydrogen or methyl
  • m 0 or 1.
  • substituted piperazinodiones of U.S. Pat. No. 3,920,659 have the formula: ##STR18## wherein R 1 and R 2 are independently of each other methyl or ethyl or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group;
  • n is an integer of from 1 to 2;
  • R 3 is an alkyl group of from 1 to 20 carbon atoms
  • R 3 is an alkylene group of from 2 to 8 carbon atoms
  • A is a straight or branched chain (lower) alkylene group containing from one to six carbon atoms with the limitation that the terminals of said alkylene group bear only hydrogen or one (lower) alkyl group.
  • R 3 is hydrogen, alkyl having one to twelve carbon atoms, ⁇ -methoxyethyl, alkenyl having three or four carbon atoms, propargyl, benzyl or alkyl-substituted benzyl;
  • R 4 is straight or branched-chain alkylene having five to eight carbon atoms, or the group (CH 2 ) m Y(CH 2 ) n wherein Y is oxygen or sulfur and m and n independently of each other are an integer from 1 to 3;
  • M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, iron, sodium, cobalt, tin, and dialkyl tin, and
  • z has a value of from 1 to 4, the value of z being the same as the available valence of M.
  • R 1 and R 2 are the same or different and each is a straight- or branched alkyl residue having from 1 to 12 carbon atoms, or R 1 and R 2 , together with the carbon atom to which they are attached, form a cycloalkyl residue having from 5 to 12 carbon atoms or the group: ##STR22## wherein R 1 and R 2 have their previous significance and Y is a straight- or branched alkyl residue having from 1 to 20 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20 carbon atoms, an aralkyl residue having from seven to twelve carbon atoms or the group --CH 2 X wherein X is the group ##STR23## wherein R 3 is hydrogen, a methyl or phenyl residue, the group ##STR24## wherein R 4 is an alkyl residue
  • R 3 is hydrogen, a straight- or branched alkyl residue having from 1 to 4 carbon atoms, an aralkyl residue having from seven to nine carbon atoms or a cycloalkyl group having from 5 or 6 carbon atoms;
  • R 4 is a metal ion or a hydrocarbyl residue having from two to twenty carbon atoms and being either unsubstituted or substituted by halogen or interrupted by one or more oxygen or sulphur atoms;
  • X is --O--, --S--, or >NR 5 , wherein R 5 has the same significance as R 3 ;
  • n 2, 3 or 4; as well as salts of the amine function of the compounds of formula I.
  • Cook U.S. Pat. No. 3,939,168 patented Feb. 17, 1976 discloses closely similar compounds having a Y substituent on the piperidyl nitrogen atom, Y being alkyl, alkenyl, aralkyl or a group ##STR26## wherein: R 7 is hydrogen, alkyl or phenyl.
  • 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylates having the formla: ##STR27## wherein: m 1 , m 3 , and m 4 are numbers from 0 to 1;
  • n 2 is a number from 1 to 2;
  • n 1 is a number from 0 to 2;
  • n 2 is a number from 0 to 3;
  • n 3 is a number from 0 to 2;
  • R 1 is selected from the group consisting of alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
  • R 2 is selected from the group consisting of alkyl; cycloalkyl; alkylaryl; aralkyl; and hydroxy-substituted such radicals;
  • R 1 and R 2 have from one to about twenty carbon atoms
  • X is hydrogen or 0 ⁇
  • Y 1 and Y 2 are bivalent linking radicals having from 1 to about 20 carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and amino-substituted such radicals;
  • Z is an organic radical having a valence from 2 to 4 and from one to about twenty carbon atoms, and selected from the group consisting of alkylene, alkylidene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; amino-substituted such radicals and 2,2,6,6-tetramethyl-4-piperidylidene;
  • Synthetic resin compositions also are provided having their resistance to deterioration in the presence of ultraviolet light enhanced by at least one of these compounds.
  • 2,2,6,6-tetramethyl-4-piperidyl aminocarboxylates having the formula: ##STR29## wherein: m 1 , m 3 and m 4 are numbers from 0 to 1;
  • n 2 is a number from 1 to 2;
  • n 1 is a number from 0 to 2;
  • n 2 is a number from 0 to 3;
  • n 3 is a number from 0 to 2;
  • R is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aralkyl, cycloalkyl, alkaryl, 2,2,6,6-tetramethyl-4-piperidyl, R 1 OOCY 2 , phenyl, hydroxy phenyl and ##STR30##
  • R 1 is selected from the group consisting of hydrogen, alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
  • R 2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and hydroxy-substituted such radicals;
  • R 1 and R 2 have from 1 to about 20 carbon atoms;
  • X is hydrogen or 0 ⁇
  • Y 1 and Y 2 are bivalent linking radicals having from one to about twenty carbon atoms, and selected from the group consisting of alkylene and cycloalkylene;
  • Z is an organic radical having a valence from 2 to 4 and having from 1 to about 20 carbon atoms, and selected from the group consisting of alkylene, alkylidene, arylene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; there being from one to four nitrogen-containing such groups, and at least one ##STR31## attached to the Z radical.
  • a preferred class of 2,2,6,6-tetramethyl-4-piperidyl aminocarboxylates are defined by the formula: ##STR32## where R, R 1 , Y 1 , Y 2 , X, m 2 , n 1 , n 2 and n 3 are as above, in Formula II.
  • Y 1 and Y 2 preferably are --CH 2 , --CH 2 CH 2 --, >CHCH 2 -- or >CHCH 2 CH 2 --, n 2 is two or three, n 1 is zero or one, and n 3 is zero, one or two, and when n 3 is one or two, R is hydrogen.
  • Z is preferably alkylene, phenylene, or alkylene-cycloalkylene.
  • Synthetic resin compositions also are provided having their resistance to deterioration in the presence of ultraviolet light enhanced by at least one of these compounds.
  • the thiocarboxylate compounds are readily prepared from the mercaptocarboxylates of 2,2,6,6-tetramethyl-piperidine-4-ol.
  • the corresponding mercaptocarboxylic acid is reacted with 2,2,6,6-tetramethyl-piperidine-4-ol to form the corresponding mercaptocarboxylate ester, and this compound is then attached to the corresponding --Z-- radical by reaction with the free mercapto group of the mercaptocarboxylate.
  • a mixture was prepared containing 20 g of the maleic acid diester of 2,2,6,6-tetramethyl-piperidine-4-ol, 29 g of lauryl thioglycolate, 20 ml of tertiary butanol, and 2 ml of a 40% methanol solution of trimethylbenzyl quaternary ammonium hydroxide. The mixture was stirred at from 30° to 35° C. for 2 hours, and then at 60° C. for an additional 4 hours.
  • the powder was oxidized with peracetic acid, yielding a yellow powder.
  • the 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylic acid esters and amino carboxylic acid esters of the invention are effective stabilizers to enhance the resistance to deterioration due to heat and/or light of synthetic polymeric materials which are susceptible to such degradation, including polyolefins such as low density polyethylene, high density polyethylene, polypropylene, polybutylene, polyisobutylene, polypentylene, and polyisopentylene, polystyrene; polydienes, such as polybutadiene and polyisoprene; and copolymers of olefins and dienes with other ethylenically and acetylenically unsaturated monomers, such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-pentene copolymers, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, acrylonitrile
  • the synthetic polymer can be in any physical form, including (for example) filaments, yarns, films, sheets, molded articles, latex, and foam.
  • the stabilizers of the invention can be employed as the sole stabilizer or, preferably, in combination with other conventional heat and light stabilizers for the particular synthetic polymer.
  • polyvinyl chloride resins other polyvinyl chloride resin heat stabilizers can be included, including polyvalent metal fatty acid salts such as barium and cadmium salts of the higher fatty acids; organic triphosphites; organotin compounds; hindered phenols; and epoxy compounds.
  • polystyrene acid salts of polyvalent metals there can be employed styrene acid salts of polyvalent metals, organic phosphites, phenolic antioxidants, and the higher fatty acid esters of thiodipropionic acids, such as, for example, dilauryl thiodipropionate.
  • polyamide stabilizers such as copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese can be used.
  • antioxidants such as hindered phenols and bis-phenols, polyvalent metal salts of the higher fatty acids, and organic phosphites can be used.
  • additives for synthetic polymers such as plasticizers, lubricants, emulsifiers, antistatic agents, flameproofing agents, pigments and fillers, can be employed.
  • a group of polyvinyl chloride resin compositions was prepared having the following formulation:
  • This formulation was blended and sheeted off on a two roll mill to form sheets 1 mm thick.
  • the light resistance of these sheets was then determined by placing strips 1 cm long in a Weather-O-Meter, and exposing them to ultraviolet light. The time in hours was then noted for the sheet to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light.
  • each of the six stabilizers in accordance with the invention is far superior to the control, a conventional ultraviolet light stabilizer for polyvinyl chloride, 2-hydroxy-4-octoxy-benzophenone.
  • Polypropylene compositions were prepared, seven stabilizers of the invention, and two of the prior art, and having the following formulation:
  • compositions were thoroughly blended in a Brabender Plastograph, and then compression-molded to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter. The time in hours required for the sheet to develop a noticeable discoloration and/or embrittlement was noted as the hours to failure. The results obtained are shown in Table II.
  • the compounds of the invention are superior stabilizers in enhancing the resistance of the polypropylene polymer composition to deterioration in the presence of ultraviolet light.
  • Ethylene-vinyl acetate copolymer compositions were prepared using stabilizers of the invention and one of the prior art, and having the following formulation:
  • the stabilizer was blended with the polymer on a two-roll mill at 120° C., and sheets 1 mm thick were then compression molded at 120° C. from the resulting blend. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. At the start and at the conclusion of the test, the tensile strength of the sheet samples was determined. The results are given in Table III as % retention of the initially determined tensile strength:
  • the stabilizer compositions in accordance with the invention are superior to 2-hydroxy-4-methoxybenzophenone in enhancing the resistance of the ethylene-vinyl acetate copolymer to deterioration in the presence of ultraviolet light.
  • High density polyethylene compositions were prepared, using seven stabilizers of the invention and two of the prior art, and having the following formulation:
  • the stabilizer was blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend. Pieces 2.5 cm square were cut off from the sheets, and exposed in a Weather-O-Meter to ultraviolet light. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure and the results are reported in Table IV:
  • the stabilizers of the invention are clearly superior to the controls in enhancing resistance of the polyethylene to degradation under ultraviolet light.
  • Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using seven stabilizers of the invention and one of the prior art, and having the following formulation:
  • the stabilizer was blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend. Pieces 2.5 cm square were cut off from the sheets, and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. Tensile strength before and after the test exposure was determined, and the results reported as the percent of tensile strength retained, at the end of this time, in Table V.
  • Polyamide resin compositions were prepared using seven stabilizers of the invention and having the following formulation:
  • the stabilizer was blended with the finely powdered polyepsilon-caprolactam in a ball mill for fifteen minutes, and the resulting powder was then compression-molded at 250° C. to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut out from the sheets, and exposed to ultraviolet light in a Weather-O-Meter for 120 hours. At the conclusion of the test period, the color of the sheets was noted. The results are given in Table VI.
  • the stabilizers of the invention are effective ultraviolet light stabilizers for polyamide resins.
  • a group of polyvinyl chloride resin compositions was prepared having the following formulation:
  • This formulation was blended and sheeted off on a two-roll mill to form sheets 1 mm thick.
  • the light resistance of these sheets was then determined by placing strips 1 cm long in a Weather-O-Meter, and exposing them to ultraviolet light. The time in hours was then noted for the sheet to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light.
  • each of the stabilizers in accordance with the invention is far superior to the control, a conventional ultraviolet light stabilizer for polyvinyl chloride, 2-hydroxy-4-octoxybenzophenone.
  • Polypropylene compositions were prepared using stabilizers of the invention and of the prior art, having the following formulation:
  • compositions were thoroughly blended in a Brabender Plastograph, and then compression-molded to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter. The time in hours required for the sheet to develop a noticeable discoloration and/or embrittlement was noted as the hours to failure. The results obtained are shown in Table VIII.
  • the compounds of the invention are superior stabilizers in enhancing the resistance of the polypropylene polymer composition to deterioration in the presence of ultraviolet light.
  • Ethylene-vinyl acetate copolymer compositions were prepared using stabilizers of the invention and one of the prior art, and having the following formulation:
  • the stabilizer was blended with the polymer on a two-roll mill at 120° C., and sheets 1 mm thick were then compression molded at 120° C. from the resulting blend. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. At the start and at the conclusion of the test, the tensile strength of the sheet samples was determined. The results are given in Table IX as % retention of the initially determined tensile strength:
  • the stabilizer compositions in accordance with the invention are superior to 2-hydroxy-4-methoxybenzophenone in enhancing the resistance of the ethylene-vinyl acetate copolymer to deterioration in the presence of ultraviolet light.
  • High density polyethylene compositions were prepared using stabilizers of the invention and of the prior art, and having the following formulation:
  • the stabilizer was blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend. Pieces 2.5 cm square were cut off from the sheets, and exposed in a Weather-O-Meter to ultraviolet light. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure and the results are reported in Table X:
  • the stabilizers of the invention are clearly superior to the controls in enhancing resistance of the polyethylene to degradation under ultraviolet light.
  • Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using stabilizers of the invention and of the prior art, and having the following formulation:
  • the stabilizer was blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend. Pieces 2.5 cm square were cut off from the sheets, and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. Tensile strength before and after the test exposure was determined, and the results reported as the percent of tensile strength retained, at the end of this time, in Table XI.
  • Polyamide resin compositions were prepared using stabilizers of the invention and having the following formulation:
  • the stabilizer was blended with the finely powdered poly-epsilon-caprolactan in a ball mill for fifteen minutes, and the resulting powder was then compression molded at 250° C. to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut out from the sheets, and exposed to ultraviolet light in a Weather-O-Meter for 120 hours. At the conclusion of the test period, the color of the sheets was noted. The results are given in Table XII:
  • the stabilizers of the invention are effective ultraviolet light stabilizers for polyamide resins.
  • Polypropylene was compounded on the mill with the additives shown in the Table below, and dumbell specimens 0.5 mm thick prepared by injection molding from the milled sheets. Percent elongation was determined on molded samples either as made or after 305 hours Weather-O-Meter exposure.
  • the nickel compound stabilized control C is green, while the other are colorless.
  • the elongation results show that the two piperidinyl esters are essentially without beneficial effect, the nickel complex has a modest beneficial effect, for which the green color must be accepted, and the thiodisuccinate ester of the invention is both more effective than the nickel complex and free of the objectionable color contribution.
  • Rectangular polypropylene samples 0.5 mm thick were irradicated with a mercury lamp with an output of radiation of 280 mm and higher wave lengths until they became brittle.
  • the formulation was the same as in the preceding experiment except for the use of 0.3 part of stabilizer. The results were as follows:
  • Example 65 The superiority of Example 65 is clear.
  • Polypropylene was compounded with a conventional heat stabilizer combination and variable light stabilizer by mixing on the mill and compression molding 0.5 mm thick panels 15 cm square at 210° C. for 6 minutes. Initial color was rated visually. 15 cm ⁇ 3 cm strips cut from the panels were exposed to light from a bank of fluorescent lamps 15 cm above the samples until failure by embrittlement.
  • the base formula was:

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Abstract

2,2,6,6-TETRAMETHYL-4-PIPERIDYL THIOCARBOXYLATES AND AMINOCARBOXYLATES ARE PROVIDED HAVING THE GENERAL FORMULA: ##STR1## wherein: M1, M3, AND M4 ARE NUMBERS FROM 0 TO 1;
m2 is a number from 1 to 2;
n1 is a number from 0 to 2;
n2 is a number from 0 to 3;
n3 is a number from 0 to 2;
R1 is selected from the group consisting of alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
R2 is selected from the group consisting of alkyl, cycloalkyl, alkylaryl, aralkyl, and hydroxy-substituted such radicals;
R1 and R2 have from one to about twenty carbon atoms;
X is hydrogen or O;
Y1 and Y2 are bivalent linking radicals having from one to about 20 carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and amino-substituted such radicals;
Q is selected from the group consisting of SR2 and ##STR2## Z is an organic radical having a valence from 2 to 4 and from one to about twenty carbon atoms, and selected from the group consisting of alkylene, alkylidene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; amino-substituted such radicals and 2,2,6,6-tetramethyl-4-piperidylidene;
There being from one to four sulfur-containing or nitrogen-containing such groups and at least one ##STR3## ATTACHED TO THE Z radical. Synthetic resin compositions also are provided having their resistance to deterioration in the presence of ultraviolet light enhanced by at least one of these compounds.

Description

Hindered 2,2,6,6-tetraalkyl-4-carboxylic acid ester piperidine compounds have been proposed by Murayama et al U.S. Pat. No. 3,640,928 patented Feb. 8, 1972 as light and heat stabilizers for synthetic polymers, such as polyolefins, polyvinyl chloride, polyvinylidene chloride, polyurethanes, and polyamides. These compounds have the general formula: ##STR4## or a salt thereof.
In the above Formula:
R1 and R2 which may be the same or different, each are an alkyl group such as methyl, ethyl, isopropyl or dodecyl, or they form, together with the carbon atom to which they are attached, a saturated alicyclic group such as: ##STR5## or a group of the formula ##STR6## n is an integer of 1 to 3 inclusive: and R3 is an acyl group.
These compounds have proved to be particularly acceptable because they do not impart a discoloration of their own to the synthetic polymer. The compounds generally employed previously have either been highly colored, such as the nickel compounds (which are normally green) and the 2-hydroxybenzophenones (which are varying shades and intensities of yellow). They also show very little tendency towards sublimation and exudation, and they have an excellent stabilizing action against both heat and light deterioration.
Consequently, the Murayama et al patent has been followed by a large number of patent and literature disclosures by Murayama et al and others of compounds including a 2,2,6,6-tetrasubstituted-4-piperidyl group attached to a base molecule of varying structures.
Murayama et al U.S. Pat. No. 3,898,303 patented Aug. 5, 1975 propose piperidino-spiro-hydantoin derivatives having the formula: ##STR7## wherein R represents an alkyl group, an alkenyl group, an alkenoyl group which may be substituted with an aryl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an acyloxyalkyl group, a cyanoalkyl group or nitroso group, and X and Y individually represent oxygen atom or sulfur atom.
Murayama et al in U.S. Pat. No. 3,899,464 patented Aug. 12, 1975 disclose a variation of the piperidino spiro compounds having the formula: ##STR8## wherein R1 represents hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, an alkynyl group, a substituted or unsubstituted aralkyl group, an aliphatic acyl group, an alkoxycarbonyl group or an aralkoxycarbonyl group, n is an integer of 1 to 4;
when n is 1, R2 represents hydrogen atom, an aliphatic, aromatic or heterocyclic monoacyl group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, an alkoxyalkyl group, an epoxyalkyl group, an alkoxysulfonylalkyl group, N-substituted carbamoyl group, a N-substituted thiocarbamoyl group, a monovalent group from an oxoacid or group ##STR9## in which
R3 represents hydrogen atom, a lower alkyl group or phenyl group and R4 represents an alkyl group;
when n is 2, R2 represents carbonyl group, an aliphatic or aromatic diacyl group, an alkylene group, an alkenylene group, an alkynylene group, an aralkylene group, a N-substituted dicarbamoyl group or a divalent group from an oxoacid;
when n is 3, R2 represents an aromatic triacyl group or a trivalent group from an oxoacid; and
when n is 4, R2 represents an aromatic tetraacyl group, and A represents a group ##STR10## in which R5 represents hydrogen atom or a lower alkyl group or, when n is 1, R5 may represent together with R2 a group ##STR11## in which R6 represents the same group as defined in R1 and may be the same or different from R1, or a group ##STR12## in which m is 1 or 2 and R7 represents hydrogen atom or, when n and m are 1, R7 represents methylene group together with R2.
Murayama et al U.S. Pat. No. 3,933,735 patented Jan. 20, 1976 propose 4-piperidone derivatives having a structure similar to the 4-piperidyl derivatives, but with a keto oxygen at the 4-position of the piperidine ring.
Murayama et al U.S. Pat. No. 3,941,744 patented Mar. 2, 1976, disclose another variation of the piperidino spiro derivatives having the formula: ##STR13## wherein R' represents an alkyl group, a substituted alkyl group, an acyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an amino group, a substituted amino group or nitroso group;
X represents oxygen atom or sulfur atom;
Y represents oxygen atom, sulfur atom or a group of the formula ═N--R" in which R" is hydrogen atom, an alkyl group or a substituted alkyl group;
Z represents oxygen atom or a group of the formula >N--R'" is hydrogen atom, an alkyl group or a substituted alkyl group;
n is an integer of 1 through 4 inclusive; and
R represents, when n is 1, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a substituted phosphino group or a substituted phosphinyl group, when n is 2, an alkylene group, an alkenylene group, an arylene group, a substituted arylene group, an aralkylene group, an alkylenediphenylene group, a bis-(acyloxyalkylene) group, an alkylene-bis-(oxycarbonylalkyl) group, a dialkylene ether group or a diphenylene ether group, when n is 3, an alkanetriyl group, a tris-(acyloxyalkylene) group, an alkane-tris-(oxycarbonylalkyl) group or a group of the group ##STR14## in which p is an integer of 1 through 8 inclusive, and when n is 4, an alkane tetrayl group, a tetrakis-(acyloxyalkylene) group or an alkanetetrakis-(oxycarbonylalkyl) group.
Murayama et al U.S. Pat. No. 3,940,363 patented Feb. 24, 1976 disclose a further variation in which two 2,2,6,6-tetrasubstituted-4-piperidyl groups are linked together via the ring nitrogen atom to an R' alkylene linking group, which may be interrupted with an oxygen or sulfur atom, an alkenylene group, an alkynylene group, an aralkylene group, an aliphatic diacyl group, a group having the formula: ##STR15## in which n is an integer of 1 or 2 and X is an alkylene group, or o-, m- or p-phenylene group or the carbon atoms of CO groups may be directly joined in the absence of X or a group of the formula: ##STR16## in which Y is an alkylene group or o-, m- or p-phenylene group.
Ramey et al U.S. Pat. Nos. 3,899,491, patented Aug. 12, 1975 and 3,920,659, patented Nov. 18, 1975, disclose alkyl alkanoate derivatives of substituted piperazines and substituted piperazinodiones. The substituted piperazines of U.S. Pat. No. 3,899,491 have the formula: ##STR17## wherein R1 and R2 are methyl or together with the carbon to which they are bound form a mono-cyclic ring system having 5 or 6 carbon atoms;
R3 is an alkyl group of from one to twenty atoms;
R4 is hydrogen or methyl, and
m is 0 or 1.
The substituted piperazinodiones of U.S. Pat. No. 3,920,659 have the formula: ##STR18## wherein R1 and R2 are independently of each other methyl or ethyl or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group;
n is an integer of from 1 to 2;
when n is 1, R3 is an alkyl group of from 1 to 20 carbon atoms;
when n is 2, R3 is an alkylene group of from 2 to 8 carbon atoms; and
A is a straight or branched chain (lower) alkylene group containing from one to six carbon atoms with the limitation that the terminals of said alkylene group bear only hydrogen or one (lower) alkyl group.
Ramey et al U.S. Pat. No. 3,920,661 patented Nov. 18, 1975 disclose dicarboxylic acids and salts in which one carboxylic acid group is esterified with a 2,2,6,6-tetrasubstituted-4-hydroxy piperidine and having the formula: ##STR19## wherein R1 and R2 independently of each other are straight- or branched-chain alkyl having from one to six carbon atoms, or together with the carbon to which they are bound form a cyclopentyl or cyclohexyl ring, which is unsubstituted or substituted with a methyl group;
R3 is hydrogen, alkyl having one to twelve carbon atoms, β-methoxyethyl, alkenyl having three or four carbon atoms, propargyl, benzyl or alkyl-substituted benzyl;
R4 is straight or branched-chain alkylene having five to eight carbon atoms, or the group (CH2)m Y(CH2)n wherein Y is oxygen or sulfur and m and n independently of each other are an integer from 1 to 3;
M is hydrogen or a metal selected from the group consisting of barium, nickel, manganese, calcium, zinc, iron, sodium, cobalt, tin, and dialkyl tin, and
z has a value of from 1 to 4, the value of z being the same as the available valence of M.
Ramey et al U.S. Pat. No. 3,939,163 patented Feb. 17, 1976 disclose closely similar compounds in which R4 is alkylene having from one to four carbon atoms.
Randell et al U.S. Pat. No. 3,939,170 patented Feb. 17, 1976 disclose dehydropyridinyl sulphides, sulphoxides and sulphones having the formula: ##STR20## wherein X is S, SO or SO2 and Y and Y1 are the same or different and each is H, OH, O- or a straight- or branched alkyl residue having from one to four carbon atoms, and salts thereof when Y and Y1 are other than O-
Randell et al in published patent application No. B408,123 published April 13, 1976 disclose substituted piperidine-4-ols having the formula: ##STR21## wherein R1 and R2 are the same or different and each is a straight- or branched alkyl residue having from 1 to 12 carbon atoms, or R1 and R2, together with the carbon atom to which they are attached, form a cycloalkyl residue having from 5 to 12 carbon atoms or the group: ##STR22## wherein R1 and R2 have their previous significance and Y is a straight- or branched alkyl residue having from 1 to 20 carbon atoms, an alkenyl or alkynyl residue having from 3 to 20 carbon atoms, an aralkyl residue having from seven to twelve carbon atoms or the group --CH2 X wherein X is the group ##STR23## wherein R3 is hydrogen, a methyl or phenyl residue, the group ##STR24## wherein R4 is an alkyl residue having from 1 to 20 carbon atoms.
Cook U.S. Pat. No. 3,929,804 patented Dec. 30, 1975 discloses 4-piperidine acetamide compounds having the formula: ##STR25## wherein R1 and R2 are the same or different and each is a straight- or branched alkyl residue having from 1 to 12 carbon atoms, or R1 and R2, together with the carbon atom to which they are attached form a cycloalkyl group having from 5 to 12 carbon atoms;
R3 is hydrogen, a straight- or branched alkyl residue having from 1 to 4 carbon atoms, an aralkyl residue having from seven to nine carbon atoms or a cycloalkyl group having from 5 or 6 carbon atoms;
R4 is a metal ion or a hydrocarbyl residue having from two to twenty carbon atoms and being either unsubstituted or substituted by halogen or interrupted by one or more oxygen or sulphur atoms;
X is --O--, --S--, or >NR5, wherein R5 has the same significance as R3 ; and
n is 2, 3 or 4; as well as salts of the amine function of the compounds of formula I.
Cook U.S. Pat. No. 3,939,168 patented Feb. 17, 1976 discloses closely similar compounds having a Y substituent on the piperidyl nitrogen atom, Y being alkyl, alkenyl, aralkyl or a group ##STR26## wherein: R7 is hydrogen, alkyl or phenyl.
In accordance with the invention, 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylates are provided having the formla: ##STR27## wherein: m1, m3, and m4 are numbers from 0 to 1;
m2 is a number from 1 to 2;
n1 is a number from 0 to 2;
n2 is a number from 0 to 3;
n3 is a number from 0 to 2;
R1 is selected from the group consisting of alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
R2 is selected from the group consisting of alkyl; cycloalkyl; alkylaryl; aralkyl; and hydroxy-substituted such radicals;
R1 and R2 have from one to about twenty carbon atoms;
X is hydrogen or 0·;
Y1 and Y2 are bivalent linking radicals having from 1 to about 20 carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and amino-substituted such radicals;
Z is an organic radical having a valence from 2 to 4 and from one to about twenty carbon atoms, and selected from the group consisting of alkylene, alkylidene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; amino-substituted such radicals and 2,2,6,6-tetramethyl-4-piperidylidene;
there being from one to four sulfur-containing such groups and at least one ##STR28## attached to the Z radical.
Synthetic resin compositions also are provided having their resistance to deterioration in the presence of ultraviolet light enhanced by at least one of these compounds.
Also provided in accordance with the invention are 2,2,6,6-tetramethyl-4-piperidyl aminocarboxylates having the formula: ##STR29## wherein: m1, m3 and m4 are numbers from 0 to 1;
m2 is a number from 1 to 2;
n1 is a number from 0 to 2;
n2 is a number from 0 to 3;
n3 is a number from 0 to 2;
R is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aralkyl, cycloalkyl, alkaryl, 2,2,6,6-tetramethyl-4-piperidyl, R1 OOCY2, phenyl, hydroxy phenyl and ##STR30## R1 is selected from the group consisting of hydrogen, alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
R2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and hydroxy-substituted such radicals;
R (when other than hydrogen), R1 and R2 have from 1 to about 20 carbon atoms;
X is hydrogen or 0·;
Y1 and Y2 are bivalent linking radicals having from one to about twenty carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and
Z is an organic radical having a valence from 2 to 4 and having from 1 to about 20 carbon atoms, and selected from the group consisting of alkylene, alkylidene, arylene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; there being from one to four nitrogen-containing such groups, and at least one ##STR31## attached to the Z radical.
A preferred class of 2,2,6,6-tetramethyl-4-piperidyl aminocarboxylates are defined by the formula: ##STR32## where R, R1, Y1, Y2, X, m2, n1, n2 and n3 are as above, in Formula II.
Y1 and Y2 preferably are --CH2, --CH2 CH2 --, >CHCH2 -- or >CHCH2 CH2 --, n2 is two or three, n1 is zero or one, and n3 is zero, one or two, and when n3 is one or two, R is hydrogen.
Another preferred class of these aminocarboxylates are defined by the formula: ##STR33## where R, R1, Y1, Y2, X, m2, n1, n2 and n3 and Z are as above, in Formula II.
Z is preferably alkylene, phenylene, or alkylene-cycloalkylene.
Synthetic resin compositions also are provided having their resistance to deterioration in the presence of ultraviolet light enhanced by at least one of these compounds.
The thiocarboxylate compounds are readily prepared from the mercaptocarboxylates of 2,2,6,6-tetramethyl-piperidine-4-ol. The corresponding mercaptocarboxylic acid is reacted with 2,2,6,6-tetramethyl-piperidine-4-ol to form the corresponding mercaptocarboxylate ester, and this compound is then attached to the corresponding --Z-- radical by reaction with the free mercapto group of the mercaptocarboxylate.
The following procedure is illustrative:
EXAMPLE I
5.5 g of benzaldehyde was added slowly to a solution of 100 ml of benzene and 23 g of the thioglycolic acid ester of 2,2,6,6-tetramethyl-piperidine-4-ol below 20° C. The mixture was stirred for 1 hour below 25° C., and an additional 2 hours at 60° C.
The solvent was then distilled off, and the resulting residue of sticky material was dissolved in n-hexane, and stored for eight days under refrigeration. White crystals were obtained, having a molecular weight of 552, corresponding to the calculated molecular weight of 551 for the compound: ##STR34##
EXAMPLE II
A mixture was prepared containing 20 g of the maleic acid diester of 2,2,6,6-tetramethyl-piperidine-4-ol, 29 g of lauryl thioglycolate, 20 ml of tertiary butanol, and 2 ml of a 40% methanol solution of trimethylbenzyl quaternary ammonium hydroxide. The mixture was stirred at from 30° to 35° C. for 2 hours, and then at 60° C. for an additional 4 hours.
The butanol and methanol were distilled off, and the resulting colorless viscous liquid was dissolved in a small amount of petroleum ether and stored for 2 days at 5° C. A white powder was obtained. The molecular weight was found to be 655, corresponding to the molecular weight calculated for the compound: ##STR35##
Using the above reaction procedures, the following additional compounds were prepared: ##STR36##
The following Example illustrates the preparation of the amino carboxylate 2,2,6,6-tetramethyl-4-piperidyl compounds:
EXAMPLE III
A mixture was prepared of 23.3 g of trimethyl nitrilo-triacetate, 61 g of 2,2,6,6-tetramethyl-piperidine-4-ol, 200 ml of xylene and 2 ml of a 12.5% methanol solution of sodium methoxide. The mixture was heated at 160° C. for 6 hours. The solvent was then distilled off, and the resulting residue was then dissolved in n-hexane, and cooled under refrigeration until white crystals were obtained. The white crystals were identified as tris-(2,2,6,6-tetramethylpiperidine-4-yl)nitrilotriacetate, melting point 124° to 126° C. All peaks in the compound's infra-red spectrum are consistent with the following structure: ##STR37##
The powder was oxidized with peracetic acid, yielding a yellow powder.
The molecular weight found for this compound was 655, corresponding to a calculated molecular weight of 654 for the compound: ##STR38##
Using the above procedure, the following compounds were prepared: ##STR39##
The 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylic acid esters and amino carboxylic acid esters of the invention are effective stabilizers to enhance the resistance to deterioration due to heat and/or light of synthetic polymeric materials which are susceptible to such degradation, including polyolefins such as low density polyethylene, high density polyethylene, polypropylene, polybutylene, polyisobutylene, polypentylene, and polyisopentylene, polystyrene; polydienes, such as polybutadiene and polyisoprene; and copolymers of olefins and dienes with other ethylenically and acetylenically unsaturated monomers, such as ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-pentene copolymers, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, synthetic rubbers of all types, such as polychloroprene; polyvinyl halides, including polyvinyl chloride homopolymer, polyvinylidene chloride; and copolymers of vinyl chloride and vinylidene chloride; vinyl chloride and vinyl acetate; vinylidene chloride and vinyl acetate; and other ethylenically unsaturated monomers; polyacetals such as polyoxymethylene and polyoxyethylene; polyesters such as polyethylene glycol-terephthalic acid ester polymers; polyamides such as polyepsiloncaprolactam; polyhexamethylene adipamide and polydecamethylene adipamide; polyurethanes; and epoxy resins.
The synthetic polymer can be in any physical form, including (for example) filaments, yarns, films, sheets, molded articles, latex, and foam.
The stabilizers of the invention can be employed as the sole stabilizer or, preferably, in combination with other conventional heat and light stabilizers for the particular synthetic polymer.
Thus, for example, in the case of polyvinyl chloride resins, other polyvinyl chloride resin heat stabilizers can be included, including polyvalent metal fatty acid salts such as barium and cadmium salts of the higher fatty acids; organic triphosphites; organotin compounds; hindered phenols; and epoxy compounds.
With polyolefin resins there can be employed styrene acid salts of polyvalent metals, organic phosphites, phenolic antioxidants, and the higher fatty acid esters of thiodipropionic acids, such as, for example, dilauryl thiodipropionate.
With polyamide resin compositions, polyamide stabilizers such as copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese can be used.
With synthetic rubbers and acrylonitrile butadiene styrene terpolymers, antioxidants such as hindered phenols and bis-phenols, polyvalent metal salts of the higher fatty acids, and organic phosphites can be used.
In addition, other conventional additives for synthetic polymers, such as plasticizers, lubricants, emulsifiers, antistatic agents, flameproofing agents, pigments and fillers, can be employed.
The following Examples in the opinion of the inventors represent preferred embodiments of synthetic resin compositions in accordance with the invention:
EXAMPLES 1 to 6
A group of polyvinyl chloride resin compositions was prepared having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Polyvinyl chloride   100                                                  
Dioctylphthalate     50                                                   
Ca stearate          1.0                                                  
Zn stearate          0.1                                                  
Stabilizer as shown in Table I                                            
                     0.1                                                  
______________________________________
This formulation was blended and sheeted off on a two roll mill to form sheets 1 mm thick. The light resistance of these sheets was then determined by placing strips 1 cm long in a Weather-O-Meter, and exposing them to ultraviolet light. The time in hours was then noted for the sheet to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light.
This test was carried out for the stabilizers having the formulae indicated in Table I. The following results were obtained:
                                  TABLE I                                 
__________________________________________________________________________
Example No.                                                               
        Stabilizer                              Hours to                  
__________________________________________________________________________
                                                Failure                   
Control 2-hydroxy-4-octoxybenzophenone          360                       
         ##STR40##                              820                       
2                                                                         
         ##STR41##                              910                       
3                                                                         
         ##STR42##                              870                       
4                                                                         
         ##STR43##                              760                       
5                                                                         
         ##STR44##                              830                       
6                                                                         
         ##STR45##                              880                       
__________________________________________________________________________
It is apparent that each of the six stabilizers in accordance with the invention is far superior to the control, a conventional ultraviolet light stabilizer for polyvinyl chloride, 2-hydroxy-4-octoxy-benzophenone.
EXAMPLES 7 to 13
Polypropylene compositions were prepared, seven stabilizers of the invention, and two of the prior art, and having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Polypropylene        100                                                  
Distearylthiodipropionate                                                 
                     0.3                                                  
Goodrite 3114 (1,3,5-tris-(3',5'-di-t-butyl                               
4'-hydroxybenzyl) isocyanurate)                                           
                     0.1                                                  
Stabilizer as shown in Table II                                           
                     0.3                                                  
______________________________________
The compositions were thoroughly blended in a Brabender Plastograph, and then compression-molded to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter. The time in hours required for the sheet to develop a noticeable discoloration and/or embrittlement was noted as the hours to failure. The results obtained are shown in Table II.
                                  TABLE II                                
__________________________________________________________________________
Example No.                                                               
        Stabilizer                            Hours to Failure            
__________________________________________________________________________
Control Tinuvin-P (2-(2'-hydroxy-5'-methylphenyl)                         
                                              340                         
        benzotriazole)                                                    
         ##STR46##                            780                         
8                                                                         
         ##STR47##                            720                         
9                                                                         
         ##STR48##                            750                         
10                                                                        
         ##STR49##                            770                         
11                                                                        
         ##STR50##                            800                         
12                                                                        
         ##STR51##                            830                         
13                                                                        
         ##STR52##                            810                         
__________________________________________________________________________
It is apparent from the above results that the compounds of the invention are superior stabilizers in enhancing the resistance of the polypropylene polymer composition to deterioration in the presence of ultraviolet light.
EXAMPLES 14 to 20
Ethylene-vinyl acetate copolymer compositions were prepared using stabilizers of the invention and one of the prior art, and having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Ethylene-vinylacetate copolymer                                           
                     100                                                  
Stabilizer as shown in Table III                                          
                     0.2                                                  
______________________________________
The stabilizer was blended with the polymer on a two-roll mill at 120° C., and sheets 1 mm thick were then compression molded at 120° C. from the resulting blend. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. At the start and at the conclusion of the test, the tensile strength of the sheet samples was determined. The results are given in Table III as % retention of the initially determined tensile strength:
                                  TABLE III                               
__________________________________________________________________________
                                                     % Retention of       
                                                     Tensile Strength     
Example No.                                                               
        Stabilizer                                   After 500            
__________________________________________________________________________
                                                     hours                
Control 2-hydroxy-4-methoxybenzophenone              72                   
14                                                                        
         ##STR53##                                   78                   
15                                                                        
         ##STR54##                                   79                   
16                                                                        
         ##STR55##                                   84                   
17                                                                        
         ##STR56##                                   83                   
18                                                                        
         ##STR57##                                   80                   
19                                                                        
         ##STR58##                                   78                   
20                                                                        
         ##STR59##                                   85                   
__________________________________________________________________________
It is apparent from the results that the stabilizer compositions in accordance with the invention are superior to 2-hydroxy-4-methoxybenzophenone in enhancing the resistance of the ethylene-vinyl acetate copolymer to deterioration in the presence of ultraviolet light.
EXAMPLES 21 to 27
High density polyethylene compositions were prepared, using seven stabilizers of the invention and two of the prior art, and having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
High density polyethylene                                                 
                     100                                                  
Stabilizer as shown in Table IV                                           
                     0.1                                                  
______________________________________
The stabilizer was blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend. Pieces 2.5 cm square were cut off from the sheets, and exposed in a Weather-O-Meter to ultraviolet light. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure and the results are reported in Table IV:
                                  TABLE IV                                
__________________________________________________________________________
Example No.                                                               
        Stabilizer                                   Hours to             
__________________________________________________________________________
                                                     Failure              
Control A                                                                 
        2-hydroxy-4-methoxybenzophenone               540                 
Control B                                                                 
        Tinuvin-P (2-(2'-hydroxy-5'-methylphenyl)     610                 
        benzotriazole)                                                    
21                                                                        
         ##STR60##                                   1030                 
22                                                                        
         ##STR61##                                   1100                 
23                                                                        
         ##STR62##                                    980                 
24                                                                        
         ##STR63##                                    950                 
25                                                                        
         ##STR64##                                   1080                 
26                                                                        
         ##STR65##                                   1120                 
27                                                                        
         ##STR66##                                   1060                 
__________________________________________________________________________
The stabilizers of the invention are clearly superior to the controls in enhancing resistance of the polyethylene to degradation under ultraviolet light.
EXAMPLES 28 to 34
Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using seven stabilizers of the invention and one of the prior art, and having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Acrylonitrile-butadiene-                                                  
                     100                                                  
styrene terpolymer                                                        
Stabilizer as shown in Table V                                            
                     0.1                                                  
______________________________________
The stabilizer was blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend. Pieces 2.5 cm square were cut off from the sheets, and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. Tensile strength before and after the test exposure was determined, and the results reported as the percent of tensile strength retained, at the end of this time, in Table V.
                                  TABLE V                                 
__________________________________________________________________________
                                       % Tensile Strength                 
Example No.                                                               
       Stabilizer                      Retained                           
__________________________________________________________________________
Control                                                                   
       2,2'-dihydroxy-4-methoxybenzophenone                               
                                       70                                 
28                                                                        
        ##STR67##                      86                                 
29                                                                        
        ##STR68##                      91                                 
30                                                                        
        ##STR69##                      90                                 
31                                                                        
        ##STR70##                      92                                 
32                                                                        
        ##STR71##                      93                                 
33                                                                        
        ##STR72##                      92                                 
34                                                                        
        ##STR73##                      91                                 
__________________________________________________________________________
It is apparent from the data that the stabilizers of the invention are superior to the 2,2'-dihydroxy-4-methoxybenzophenone of the prior art.
EXAMPLES 35 to 41
Polyamide resin compositions were prepared using seven stabilizers of the invention and having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Poly-epsilon-caprolactam                                                  
                     100                                                  
Stabilizer as shown in Table VI                                           
                     0.1                                                  
______________________________________
The stabilizer was blended with the finely powdered polyepsilon-caprolactam in a ball mill for fifteen minutes, and the resulting powder was then compression-molded at 250° C. to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut out from the sheets, and exposed to ultraviolet light in a Weather-O-Meter for 120 hours. At the conclusion of the test period, the color of the sheets was noted. The results are given in Table VI.
                                  TABLE VI                                
__________________________________________________________________________
Example No.                                                               
       Stabilizer                         Color of Sheet                  
__________________________________________________________________________
Control                                                                   
       None                               Yellow                          
35                                                                        
        ##STR74##                                                         
36                                                                        
        ##STR75##                         Pale Yellow                     
37                                                                        
        ##STR76##                         None                            
38                                                                        
        ##STR77##                         None                            
39                                                                        
        ##STR78##                         None                            
40                                                                        
        ##STR79##                         None                            
41                                                                        
        ##STR80##                         None                            
__________________________________________________________________________
It is apparent that the stabilizers of the invention are effective ultraviolet light stabilizers for polyamide resins.
EXAMPLES 42 to 45
A group of polyvinyl chloride resin compositions was prepared having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Polyvinyl chloride   100                                                  
Dioctylphthalate     50                                                   
Ca stearate          1.0                                                  
Zn stearate          0.1                                                  
Stabilizer as shown in Table I                                            
                     0.1                                                  
______________________________________
This formulation was blended and sheeted off on a two-roll mill to form sheets 1 mm thick. The light resistance of these sheets was then determined by placing strips 1 cm long in a Weather-O-Meter, and exposing them to ultraviolet light. The time in hours was then noted for the sheet to develop a noticeable discoloration and/or embrittlement, indicating deterioration due to oxidation in the presence of ultraviolet light.
This test was carried out for the stabilizers having the formulae indicated in Table VII. The following results were obtained:
                                  TABLE VII                               
__________________________________________________________________________
Example No.                                                               
        Stabilizer                Hours to Failure                        
__________________________________________________________________________
Control 2-hydroxy-4-octoxybenzophenone                                    
                                  360                                     
42                                                                        
         ##STR81##                650                                     
43                                                                        
         ##STR82##                800                                     
44                                                                        
         ##STR83##                780                                     
45                                                                        
         ##STR84##                840                                     
__________________________________________________________________________
It is apparent that each of the stabilizers in accordance with the invention is far superior to the control, a conventional ultraviolet light stabilizer for polyvinyl chloride, 2-hydroxy-4-octoxybenzophenone.
EXAMPLES 46 to 49
Polypropylene compositions were prepared using stabilizers of the invention and of the prior art, having the following formulation:
______________________________________                                    
Ingredient           Parts by Weight                                      
______________________________________                                    
Polypropylene        100                                                  
Distearylthiodipropionate                                                 
                     0.3                                                  
Goodrite 3114 (1,3,5-tris-(3',5'-di-t-butyl                               
                     0.1                                                  
4'-hydroxybenzyl) isocyanurate)                                           
Stabilizer as shown in Table VIII                                         
                     0.3                                                  
______________________________________
The compositions were thoroughly blended in a Brabender Plastograph, and then compression-molded to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter. The time in hours required for the sheet to develop a noticeable discoloration and/or embrittlement was noted as the hours to failure. The results obtained are shown in Table VIII.
                                  TABLE VIII                              
__________________________________________________________________________
Example                                                  Hours            
No.  Stabilizer                                          to               
__________________________________________________________________________
                                                         Failure          
Control                                                                   
     Tinuvin-P (2-(2'-hydroxy-5'-                        340              
     methylphenyl)benzotriazole)                                          
46                                                                        
      ##STR85##                                          760              
47                                                                        
      ##STR86##                                          800              
48                                                                        
      ##STR87##                                          740              
49                                                                        
      ##STR88##                                          760              
__________________________________________________________________________
It is apparent from the above results that the compounds of the invention are superior stabilizers in enhancing the resistance of the polypropylene polymer composition to deterioration in the presence of ultraviolet light.
EXAMPLES 50 to 54
Ethylene-vinyl acetate copolymer compositions were prepared using stabilizers of the invention and one of the prior art, and having the following formulation:
______________________________________                                    
Ingredient             Parts by Weight                                    
______________________________________                                    
Ethylene-vinylacetate copolymer                                           
                      100                                                 
Stabilizer as shown in Table IX                                           
                      0.2                                                 
______________________________________
The stabilizer was blended with the polymer on a two-roll mill at 120° C., and sheets 1 mm thick were then compression molded at 120° C. from the resulting blend. Pieces 2.5 cm square were cut off from the sheets and exposed to ultraviolet light in a Weather-O-Meter for 500 hours. At the start and at the conclusion of the test, the tensile strength of the sheet samples was determined. The results are given in Table IX as % retention of the initially determined tensile strength:
                                  TABLE IX                                
__________________________________________________________________________
                                           % Retention of                 
Example                                    Tensile Strength               
No.  Stabilizer                            After 500 hours                
__________________________________________________________________________
Control                                                                   
     2-hydroxy-4-methoxybenzophenone       72                             
50                                                                        
      ##STR89##                            81                             
51                                                                        
      ##STR90##                            80                             
52                                                                        
      ##STR91##                            77                             
53                                                                        
      ##STR92##                            81                             
54                                                                        
      ##STR93##                            82                             
__________________________________________________________________________
It is apparent from the results that the stabilizer compositions in accordance with the invention are superior to 2-hydroxy-4-methoxybenzophenone in enhancing the resistance of the ethylene-vinyl acetate copolymer to deterioration in the presence of ultraviolet light.
EXAMPLES 55 to 57
High density polyethylene compositions were prepared using stabilizers of the invention and of the prior art, and having the following formulation:
______________________________________                                    
Ingredient            Parts by Weight                                     
______________________________________                                    
High density polyethylene                                                 
                      100                                                 
Stabilizer as shown in Table X                                            
                      0.1                                                 
______________________________________
The stabilizer was blended with the polymer on a two-roll mill and sheets 0.5 mm thick were prepared by compression molding of the blend. Pieces 2.5 cm square were cut off from the sheets, and exposed in a Weather-O-Meter to ultraviolet light. The time in hours when degradation set in, as determined by a significant discoloration and/or embrittlement, was noted as hours to failure and the results are reported in Table X:
                                  TABLE X                                 
__________________________________________________________________________
Example No.                                                               
       Stabilizer                            Hours to Failure             
__________________________________________________________________________
Control A                                                                 
       2-hydroxy-4-methoxybenzophenone        540                         
Control B                                                                 
       Tinuvin-P(2-(2'-hydroxy-5'-                                        
       methylphenyl)benzotriazole)            610                         
55                                                                        
        ##STR94##                            1050                         
56                                                                        
        ##STR95##                            1150                         
57                                                                        
        ##STR96##                            1090                         
__________________________________________________________________________
The stabilizers of the invention are clearly superior to the controls in enhancing resistance of the polyethylene to degradation under ultraviolet light.
EXAMPLES 58 to 61
Acrylonitrile-butadiene-styrene terpolymer resin compositions were prepared using stabilizers of the invention and of the prior art, and having the following formulation:
______________________________________                                    
Ingredient              Parts by Weight                                   
______________________________________                                    
Acrylonitrile-butadiene-styrene terpolymer                                
                        100                                               
Stabilizer as shown in Table XI                                           
                        0.1                                               
______________________________________
The stabilizer was blended with the resin on a two-roll mill, and sheets 3 mm thick were prepared by compression molding of the resulting blend. Pieces 2.5 cm square were cut off from the sheets, and subjected to ultraviolet light in a Weather-O-Meter for 800 hours. Tensile strength before and after the test exposure was determined, and the results reported as the percent of tensile strength retained, at the end of this time, in Table XI.
                                  TABLE XI                                
__________________________________________________________________________
                                                       % Tensile          
                                                       Strength           
Ex. No.                                                                   
     Stabilizer                                        Retained           
__________________________________________________________________________
Control                                                                   
     2,2'-dihydroxy-4-methoxybenzophenone              70                 
58                                                                        
      ##STR97##                                        87                 
59                                                                        
      ##STR98##                                        87                 
60                                                                        
      ##STR99##                                        90                 
61                                                                        
      ##STR100##                                       91                 
__________________________________________________________________________
It is apparent from the data that the stabilizers of the invention are superior to the 2,2'-dihydroxy-4-methoxybenzophenone of the prior art.
EXAMPLES 62 and 63
Polyamide resin compositions were prepared using stabilizers of the invention and having the following formulation:
______________________________________                                    
Ingredient            Parts by Weight                                     
______________________________________                                    
Poly-epsilon-caprolactam                                                  
                      100                                                 
Stabilizer as shown in Table XII                                          
                      0.1                                                 
______________________________________
The stabilizer was blended with the finely powdered poly-epsilon-caprolactan in a ball mill for fifteen minutes, and the resulting powder was then compression molded at 250° C. to form sheets 0.5 mm thick. Pieces 2.5 cm square were cut out from the sheets, and exposed to ultraviolet light in a Weather-O-Meter for 120 hours. At the conclusion of the test period, the color of the sheets was noted. The results are given in Table XII:
                                  TABLE XII                               
__________________________________________________________________________
Example No.                                                               
       Stabilizer                            Color of Sheet               
__________________________________________________________________________
Control                                                                   
       None                                  Yellow                       
62                                                                        
        ##STR101##                           Pale Yellow                  
63                                                                        
        ##STR102##                           None                         
__________________________________________________________________________
It is apparent that the stabilizers of the invention are effective ultraviolet light stabilizers for polyamide resins.
EXAMPLE 64
Polypropylene was compounded on the mill with the additives shown in the Table below, and dumbell specimens 0.5 mm thick prepared by injection molding from the milled sheets. Percent elongation was determined on molded samples either as made or after 305 hours Weather-O-Meter exposure.
______________________________________                                    
Ingredient            Parts by Weight                                     
______________________________________                                    
Polypropylene (Profax 6501)                                               
                      100                                                 
n-Octadecyl-beta-(4-hydroxy-3,5-di-t-                                     
                      0.1                                                 
butylphenyl)propionate                                                    
Dilauryl thiodipropionate                                                 
                      0.3                                                 
Stabilizer listed in Table XIII                                           
                      0.1                                                 
______________________________________
The measured elongations before and after Weather-O-Meter exposure for 305 hours are tabulated in Table XIII:
              TABLE XIII                                                  
______________________________________                                    
                                    %                                     
                           %        Elong-                                
                           Elong-   ation                                 
Ex.                        ation    after 305                             
No.     Stabilizer         Initial  hours                                 
______________________________________                                    
        None               344      4.4                                   
Control 2,2,6,6-tetramethyl-                                              
                           193      3.3                                   
A       piperidine-                                                       
        4-yl benzoate                                                     
Control Bis (2,2,6,6-tetramethyl-                                         
                           308      3.9                                   
B       piperidine-                                                       
        4-yl)sebacate                                                     
Control 2,2'-thiobis (p-t-octylphenol)                                    
C       n-butylamine nickel complex                                       
                           326      8.2                                   
64      Tetrakis (2,2,6,6-tetramethyl-                                    
                           297      18.3                                  
        piperidine-4-yl) thiodisuccinate                                  
        (compound No. 34)                                                 
______________________________________
The differences in initial elongation are not significant since elongation is very sensitive to imperfections in the samples.
The nickel compound stabilized control C is green, while the other are colorless. The elongation results show that the two piperidinyl esters are essentially without beneficial effect, the nickel complex has a modest beneficial effect, for which the green color must be accepted, and the thiodisuccinate ester of the invention is both more effective than the nickel complex and free of the objectionable color contribution.
EXAMPLE 65
Rectangular polypropylene samples 0.5 mm thick were irradicated with a mercury lamp with an output of radiation of 280 mm and higher wave lengths until they became brittle. The formulation was the same as in the preceding experiment except for the use of 0.3 part of stabilizer. The results were as follows:
              TABLE XIV                                                   
______________________________________                                    
Ex.                          Hours to                                     
No.     Stabilizer           Embrittlement                                
______________________________________                                    
        None                 72                                           
Control Bis(2,2,6,6-tetramethylpiperidine-                                
                             216                                          
A       4-yl)sebacate                                                     
65      tris(2,2,6,6-tetramethylpiperidine-                               
                             425                                          
        4-yl)nitrilotriacetate                                            
______________________________________
The superiority of Example 65 is clear.
EXAMPLE 66
Polypropylene was compounded with a conventional heat stabilizer combination and variable light stabilizer by mixing on the mill and compression molding 0.5 mm thick panels 15 cm square at 210° C. for 6 minutes. Initial color was rated visually. 15 cm × 3 cm strips cut from the panels were exposed to light from a bank of fluorescent lamps 15 cm above the samples until failure by embrittlement.
The base formula was:
              TABLE XV                                                    
______________________________________                                    
Ingredient              Parts by Weight                                   
______________________________________                                    
Polypropylene (Profax 6501)                                               
                        100                                               
Tris (3,5-di-t-butyl-4-hydroxybenzyl)                                     
                        0.15                                              
isocyanurate                                                              
Distearyl thiodipropionate                                                
                        0.3                                               
Stabilizer listed in Table XVI                                            
                        0.5                                               
______________________________________
Initial color, time to embrittlement in the Weather-O-Meter and heat stability, i.e. time to failure in a 150° air oven, are tabulated in Table XVI for each sample.
              TABLE XVI                                                   
______________________________________                                    
                               Hours to                                   
                                      Hours to                            
                               failure                                    
                                      Em-                                 
      Light           Initial  at     brittle-                            
Ex.   Stabilizer      Color    150° C.                             
                                      ment                                
______________________________________                                    
      None            Color-   3850    370                                
                      less                                                
Con-  2-hydroxy-4-n-octyl-                                                
                      Slightly 3140   1900                                
trol  oxybenzophenone 0.5                                                 
                      Yellow                                              
66    2-hydroxy-4-n-octyl-                                                
      oxybenzophenone 0.3                                                 
      Tris (2,2,6,6-tetra-                                                
                      Color-   4075   2175                                
      methylpiperidine 4-yl)                                              
                      less                                                
      nitrilotriacetate 0.2                                               
______________________________________
These results show that with the conventional benzophenone type light stabilizer the beneficial effect on light stability is compensated by a sacrifice in early color and heat stability. With the inclusion of the amino acid ester of this invention in the combination, initial color and heat stability are at least as good as in the control and outstanding light stability is achieved.

Claims (58)

Having regard to the foregoing disclosures, the following is claimed as the inventive and patentable embodiments thereof:
1. A 2,2,6,6-tetramethyl-4-piperidyl thiocarboxylates are provided having the general formula: ##STR103## wherein: m1, m3, and m4 are numbers from 0 to 1;
m2 is a number from 1 to 2;
n1 is a number from 0 to 2;
n2 is a number from 0 to 3;
n3 is a number from 0 to 2;
R1 is selected from the group consisting of alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
R2 is selected from the group consisting of alkyl, cycloalkyl, alkaryl, aralkyl, and hydroxy-substituted such radicals;
R1 and R2 have from one to about twenty carbon atoms;
X is hydrogen or O.sub.. ;
Y1 and Y2 are bivalent linking radicals having from one to about twenty carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and amino-substituted such radicals;
Z is an organic radical having a valence from 2 to 4 and from one to about twenty carbon atoms, and selected from the group consisting of alkylene, alkylidene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene; amino-substituted such radicals and 2,2,6,6-tetramethyl-4-piperidylidene;
there being from one to four sulfur-containing such groups and at least one ##STR104## attached to the Z radical.
2. A compound according to claim 1 in which n1 and n3 are each zero, and n2 is from 2 to 3.
3. A compound according to claim 1 in which n1 and n2 are each one or two, and n3 is zero.
4. A compound according to claim 1 in which n2 and n3 are each one or two, and n1 is zero.
5. A compound according to claim 1 in which X is hydrogen.
6. A compound according to claim 1 in which X is O.sup...
7. A compound according to claim 1 in which Y1 and Y2 are each alkylene.
8. A compound according to claim 1 in which Y1 and Y2 are each cycloalkylene.
9. A compound according to claim 1 in which Z is alkylene.
10. A compound according to claim 1 in which Z is alkylidene.
11. A compound according to claim 1 in which Z is phenylalkylidene.
12. A compound according to claim 1 in which there is one sulfur-containing such radical.
13. A compound according to claim 1 in which there are two sulfur-containing such radicals.
14. A compound according to claim 1 in which there are three sulfur-containing such radicals.
15. A compound according to claim 1 in which n1 and n2 are each one or two, n3 is zero, Y1 and Y2 are each alkylene, Z is alkylene, and m4 is one.
16. A compound according to claim 1 in which n1 and n3 are each zero, n2 is one to three, Z is alkylene and Y2 is alkylene, and m4 is one.
17. A compound according to claim 1 having the formula: ##STR105##
18. A compound according to claim 1 having the formula: ##STR106##
19. A polyvinyl chloride resin composition having improved resistance to deterioration when heated at 350° F, comprising a polyvinyl chloride resin formed at least in part of the recurring group ##STR107## and having a chlorine content in excess of 40 percent, where X is either hydrogen or chlorine; and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
20. A polyvinyl chloride resin composition in accordance with claim 19, in which the polyvinyl chloride resin is polyvinyl chloride homopolymer.
21. A polyvinyl chloride resin composition in accordance with claim 19, in which the polyvinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate.
22. An olefin polymer composition having improved resistance to deterioration comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from two to six carbon atoms and polystyrene, and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
23. An olefin polymer composition in accordance with claim 22 wherein the polyolefin is polypropylene.
24. An olefin polymer composition in accordance with claim 22 wherein the polyolefin is polyethylene.
25. An acrylonitrile-butadiene-styrene polymer having improved resistance to deterioration when heated at 300° F and above and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
26. A synthetic rubbery diene polymer composition having improved resistance to deterioration comprising a rubbery diene polymer and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
27. A polyamide resin composition having improved resistance to deterioration comprising a polyamide resin and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
28. An ethylene-vinyl acetate copolymer composition having improved resistance to deterioration comprising an ethylene-vinyl acetate copolymer and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 1.
29. A 2,2,6,6-tetramethyl-4-piperidyl aminocarboxylate having the formula: ##STR108## wherein: m1, m3 and m4 are numbers from 0 to 1;
m2 is a number from 1 to 2;
n1 is a number from 0 to 2;
n2 is a number from 0 to 3;
n3 is a number from 0 to 2;
R is selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aralkyl, cycloalkyl, alkaryl, 2,2,6,6-tetramethyl-4-piperidyl, R1 OOCY2, phenyl, hydroxy phenyl and ##STR109## R1 is selected from the group consisting of hydrogen, alkyl, aralkyl, cycloalkyl and 2,2,6,6-tetramethyl-4-piperidyl;
R2 is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and hydroxy-substituted such radicals;
R (when other than hydrogen), R1 and R2 have from one to about twenty carbon atoms;
X is hydrogen or O.sup.. ;
Y1 and Y2 are bivalent linking radicals having from one to about twenty carbon atoms, and selected from the group consisting of alkylene and cycloalkylene; and
Z is an organic radical having a valence from 2 to 4 and having from one to about twenty carbon atoms, and selected from the group consisting of alkylene, alkylidene, arylene, aralkylene, aralkylidene, alkarylene, alkarylidene, heterocycloalkylene, heterocycloalkylidene, cycloalkylene and cycloalkylidene;
there being from one to four nitrogen-containing such groups, and at least one ##STR110## attached to the Z radical.
30. A compound according to claim 29 in which n1 and n3 are each zero, and n2 is from 2 to 3.
31. A compound according to claim 29, in which n1 and n2 are each one or two, and n3 is zero.
32. A compound according to claim 29 in which n2 and n3 are each one or two, and n1 is zero.
33. A compound according to claim 29 in which X is hydrogen.
34. A compound according to claim 29 in which X is O.sup...
35. A compound according to claim 29 in which Y1 and Y2 are each alkylene.
36. A compound according to claim 1 in which Z is alkylene.
37. A compound according to claim 29 in which Z is alkylidene.
38. A compound according to claim 29 in which there is one nitrogen-containing such radical.
39. A compound according to claim 29 in which there are two nitrogen-containing such radicals.
40. A compound according to claim 29 in which there are three nitrogen-containing such radicals.
41. A compound according to claim 29 having the formula: ##STR111##
42. A compound according to claim 29 having the formula: ##STR112##
43. A compound according to claim 29 having the formula: ##STR113##
44. A compound according to claim 29 having the formula: ##STR114##
45. A compound according to claim 29 having the formula: ##STR115##
46. A compound according to claim 29 having the formula: ##STR116##
47. A polyvinyl chloride resin composition having improved resistance to deterioration when heated at 350° F, comprising a polyvinyl chloride resin formed at least in part of the recurring group ##STR117## and having a chlorine content in excess of 40 percent, where X is either hydrogen or chlorine; and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
48. A polyvinyl chloride resin composition in accordance with claim 47, in which the polyvinyl chloride resin is polyvinyl chloride homopolymer.
49. A polyvinyl chloride resin composition in accordance with claim 47, in which the polyvinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate.
50. An olefin polymer composition having improved resistance to deterioration comprising an olefin polymer selected from the group consisting of polymers of alpha-olefins having from 2 to 6 carbon atoms and polystyrene, and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
51. An olefin polymer composition in accordance with claim 50 wherein the polyolefin is polypropylene.
52. An olefin polymer composition in accordance with claim 50 wherein the polyolefin is polyethylene.
53. An acrylonitrile-butadiene-styrene polymer having improved resistance to deterioration when heated at 300° F and above and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
54. A synthetic rubbery diene polymer composition having improved resistance to deterioration comprising a rubbery diene polymer and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
55. A polyamide resin composition having improved resistance to deterioration comprising a polyamide resin and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
56. An ethylene-vinyl acetate copolymer composition having improved resistance to deterioration comprising an ethylene-vinyl acetate copolymer and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 29.
57. A polyvinyl chloride resin composition having improved resistance to deterioration when heated at 350° F, comprising a polyvinyl chloride resin formed at least in part of the recurring group ##STR118## and having a chlorine content in excess of 40 percent, where X is either hydrogen or chlorine; and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 41.
58. A polyvinyl chloride resin composition having improved resistance to deterioration when heated at 350° F, comprising a polyvinyl chloride resin formed at least in part of the recurring group ##STR119## and having a chlorine content in excess of 40 percent, where X is either hydrogen or chlorine; and an amount to improve resistance to deterioration of the resin of a compound in accordance with claim 42.
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US4369321A (en) * 1979-12-21 1983-01-18 Chimosa Chimica Organica S.P.A. Piperidine derivatives which are stabilizers for synthetic polymers
US4619958A (en) * 1982-10-02 1986-10-28 Adeka Argus Chemical Co., Ltd. Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers
JPS6233153A (en) * 1985-08-07 1987-02-13 Sumitomo Chem Co Ltd Piperidine derivatives, their production methods, and stabilizers for organic substances containing them as active ingredients
US4691015A (en) * 1984-07-23 1987-09-01 Ciba-Geigy Corporation Hydroxylamines derived from hindered amines
EP0291916A1 (en) * 1987-05-19 1988-11-23 Fujisawa Pharmaceutical Co., Ltd. Dithioacetal compounds, processes for preparation thereof and pharmaceutical composition comprising the same
EP0389424A1 (en) * 1989-03-21 1990-09-26 Ciba-Geigy Ag 1-Hydrocarbyloxy hindered amine mercaptoacid esters, thioacetals, sulfides and disulfides
US5026750A (en) * 1989-03-21 1991-06-25 Ciba-Geigy Corporation 1-hydrocarbyloxy hindered amine mercaptoacid esters, thioacetals, sulfides and disulfides
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EP0550001A1 (en) * 1991-12-26 1993-07-07 Mitsubishi Chemical Corporation Cyclohexylamine derivatives
EP0634412A1 (en) * 1993-07-16 1995-01-18 Ciba-Geigy Ag Piperidine compounds for use as stabilizers for organic materials
US5449776A (en) * 1993-06-03 1995-09-12 Ciba-Geigy Corporation Piperidine-triazine compounds for use as light stabilizers, heat stabilizers and oxidation stabilizers for organic materials
US5457143A (en) * 1991-06-04 1995-10-10 Ciba-Geigy Corporation Stabilization of polymeric organic materials by using synergistic mixtures comprising sterically hindered cyclic amines and derivatives of 3-pyrazolidinone or 1,2,4-triazolidine-3,5-dione
WO2001062710A1 (en) * 2000-02-22 2001-08-30 Basf Aktiengesellschaft Stabilizing agent for hydroxylamine solutions
CN111499564A (en) * 2019-01-30 2020-08-07 北京八亿时空液晶科技股份有限公司 Novel light stabilizer compound and preparation method and application thereof

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EP0031304B1 (en) * 1979-12-21 1984-06-13 CIBA-GEIGY S.p.A. Piperidine derivatives as stabilizers for synthetic polymers
US4501837A (en) * 1979-12-21 1985-02-26 Ciba-Geigy S.P.A. Piperidine derivatives which are stabilisers for synthetic polymers
US4525503A (en) * 1979-12-21 1985-06-25 Ciba-Geigy S.P.A. Piperidine derivatives which are stabilizers for synthetic polymers
US4369321A (en) * 1979-12-21 1983-01-18 Chimosa Chimica Organica S.P.A. Piperidine derivatives which are stabilizers for synthetic polymers
US4619958A (en) * 1982-10-02 1986-10-28 Adeka Argus Chemical Co., Ltd. Mixed 2,2,6,6-tetramethyl piperidinyl carboxylic acid ester and amide light stabilizers and stabilized synthetic polymers
US4691015A (en) * 1984-07-23 1987-09-01 Ciba-Geigy Corporation Hydroxylamines derived from hindered amines
JPS6233153A (en) * 1985-08-07 1987-02-13 Sumitomo Chem Co Ltd Piperidine derivatives, their production methods, and stabilizers for organic substances containing them as active ingredients
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